US3450740A - Preparation of polyhalogenated phenylene polyisocyanates - Google Patents

Preparation of polyhalogenated phenylene polyisocyanates Download PDF

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Publication number
US3450740A
US3450740A US473818A US3450740DA US3450740A US 3450740 A US3450740 A US 3450740A US 473818 A US473818 A US 473818A US 3450740D A US3450740D A US 3450740DA US 3450740 A US3450740 A US 3450740A
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US
United States
Prior art keywords
polyhalogenated
phosgene
diamine
polyisocyanates
phenylene
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Expired - Lifetime
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US473818A
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English (en)
Inventor
David F Gavin
Ehrenfried H Kober
Wilhelm J Schnabel
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Olin Corp
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Olin Corp
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Publication date
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Publication of US3450740A publication Critical patent/US3450740A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/773—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene

Definitions

  • Polyhalogenated phenylene polyisocyanates are prepared by simultaneously introducing a solution of a polyhalogenated phenylene polyamine having a halogen in each position ortho to an amino group, in an inert solvent and phosgene into a reactor and then reacting the polyamine and the phosgene at a temperature of about 130 to 180 C.
  • This invention relates to polyhalogenated aromatic polyisocyanates and to a process for their preparation. More particularly, this invention relates to a process of preparing polyhalogenated aromatic polyisocyanates in high yields by phosgenation of polyhalogenated aromatic polyamines.
  • phosgenation under conditions of the conventional two-step, cold-hot phosgenation, of highly chlorinated aromatic polyamines, in which each position ortho to an amino group is substituted :by halogen, such as 2,4,fi-trichlorophenylene-1,3-diamine, 2,4,5,6 tetrachlorophenylene-1,3-diamine, 2,3,5,6 tetrachlorophenylene 1,4-diamine and a series of chlorinated aromatic triamines as well as the corresponding brominated diamines and triamines results predominantly in only partial conversion of the amino groups with the formation of aminoarylisocyanates as described in US. Patent 2,884,435.
  • halogen such as 2,4,fi-trichlorophenylene-1,3-diamine, 2,4,5,6 tetrachlorophenylene-1,3-diamine, 2,3,5,6 tetrachlorophenylene 1,4-diamine and a series of chlorinated aromatic
  • Polyisocyanates derived from a complete conversion of all amino groups present in the original polyhalogenated polyamines subjected to the phosgenation are formed only in small amounts as by-products. It has been found surprisingly that phosgenation of polyhalogenated polyamines in which each position ortho to an amino group is vsubstituted by a halogen, according to this invention, results in complete conversion of all amino groups to isocyanato groups to give halogenated polyisocyanates.
  • the phosgenation process of this invention is conducted by introducing a solution of the polyamine in an inert solvent at elevated temperature into a phosgenation reactor and feeding simultaneously an excess of phosgene into the reactor.
  • Gaseous phosgene or liquid phosgene can be employed.
  • the temperature during the phosgenation is maintained at about 130-180 C., preferably at 160-170" C.
  • Atmospheric pressure or super atmospheric pressure up to about 150 p.s.i. or more can be applied.
  • Monoor dichlorobenzene, a-chloronaphthalene, xylene, aromatic and aliphatic carbonic acid esters, ketones, etc. are suitable inert organic solvents.
  • an excess of phosgene ranging from 2-10 moles of phosgene to each amino group equivalent can be employed.
  • the excess of phosgene and the hydrogen chloride formed can be removed by any conventional method, such as by purging the reaction mixture at an elevated temperature with an inert gas, e.'g. nitrogen, carbon dioxide, etc.
  • an inert gas e.'g. nitrogen, carbon dioxide, etc.
  • the formed polyisocyanates are isolated by fractional distillation, by crystallization or by any of the other methods well known in the art.
  • Polyhalogenated aromatic polyamines useful as starting materials in the process of this invention include those aromatic polyamines in which each position ortho to an amino group is substituted by a halogen selected from the group consisting of chlorine, bromine and fluorine.
  • Suitable aromatic polyamines include 2,4,6-trichlorophenylene-1,3-diamine; 2,4,5,-6-tetrachloro- 1,3 diamine; 2,3,5,6-tetrachloro-1,4-diamine; 2,4,6-trichlorophenylene- 1,3,5-triamine, etc., and the corresponding bromine and fluorine derivatives.
  • the process of this invention can be operated either as a batch or continuous process.
  • EXAMPLE I The apparatus utilized in this experiment was a 4,000 ml. fullybafiled, resin reaction kettle equipped with a turbine type agitator, a thermometer, a reflux condensor, a phosgene inlet and an inlet for the amine feed solution. Both inlets dip below the stirrer.
  • o-Dichlorobenzene 1000 ml. was placed in the reactor and saturated with phosgene at 160 C.
  • an excess of gaseous phosgene was fed into the reaction mixture at a rate corresponding to a phosgene: diamine mol ratio of 8:1.
  • the reaction mixture was stirred at approx. 1500 r.p.m.
  • novel polyisocyanates of this invention can be reacted with polyether polyols, such as propoxylated glycerol of molecular weight of 3000 and in the presence of suitable catalysts and blowing agents to form :a highly flame resistant polyurethane foam.
  • polyether polyols such as propoxylated glycerol of molecular weight of 3000
  • a process for preparing a polyhalogenated phenylene polyisocyanate which comprises simultaneously introducing (1) a solution of a polyhalogenated phenylene polyamine having in each position ortho to an amino group a halogen selected from the group consisting of chlorine, bromine and fluorine, in an inert organic solvent and (2) phosgene into a reactor and therein reacting with mixing at a temperature of from about to C., the said diamine and phosgene to yield the corresponding polyhalogenated phenylene polyisocyanate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyurethanes Or Polyureas (AREA)
US473818A 1965-07-21 1965-07-21 Preparation of polyhalogenated phenylene polyisocyanates Expired - Lifetime US3450740A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US47381865A 1965-07-21 1965-07-21

Publications (1)

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US3450740A true US3450740A (en) 1969-06-17

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US473818A Expired - Lifetime US3450740A (en) 1965-07-21 1965-07-21 Preparation of polyhalogenated phenylene polyisocyanates

Country Status (7)

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US (1) US3450740A (enrdf_load_stackoverflow)
BE (1) BE684377A (enrdf_load_stackoverflow)
DE (1) DE1593219C3 (enrdf_load_stackoverflow)
ES (1) ES329268A1 (enrdf_load_stackoverflow)
FR (1) FR1486259A (enrdf_load_stackoverflow)
GB (1) GB1110191A (enrdf_load_stackoverflow)
NL (1) NL6610199A (enrdf_load_stackoverflow)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683160A (en) * 1953-03-19 1954-07-06 Du Pont Preparation of aromatic isocyanates

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2683160A (en) * 1953-03-19 1954-07-06 Du Pont Preparation of aromatic isocyanates

Also Published As

Publication number Publication date
ES329268A1 (es) 1967-05-01
NL6610199A (enrdf_load_stackoverflow) 1967-01-23
DE1593219C3 (de) 1975-09-18
DE1593219B2 (de) 1975-01-23
DE1593219A1 (de) 1970-06-18
GB1110191A (en) 1968-04-18
BE684377A (enrdf_load_stackoverflow) 1967-01-20
FR1486259A (fr) 1967-06-23

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